She started modeling when she was 13, the same year Aoki was introduced by her godmother to Kate Moss, who would later take the young model under her wing. She was signed to Storm Model Management at age 14. In 1998, at the age of 16, Aoki replaced Naomi Campbell as the face of Versace.[1]

Aoki has joined L.A.'s International Creative Management for representation and The Firm for management, and has been on the cover of I-D magazine three times. She was also the face of Lancome cosmetics for four years. Aoki posed for Singaporean photographer Leslie Kee for Kee's 2006 charity photo-book "Super Stars", dedicated to the victims of the 2004 Asian tsunami disaster, which consists of photographs of 300 Asian celebrities by Kee. The same year, Aoki posed for photographer Marc Baptiste’s book Nudes wearing a dress. In September 2007, it was announced she was designing a jeans line for Levi's Asian market.[5] Aoki made a return to the runway, walking for the Chanel Pre-Fall 2008 show in London and the couture show in Paris where she was the bride. She is signed to 1/One Management New York, d-Management (Milan), and City (Paris).

Her half-brother, Steve Aoki, is a Los AngelesDJ and the founder of Dim Mak Records. As of January 2011, Aoki was engaged to James Bailey.[6] She gave birth to their first child, Hunter, in June 2011.[7] On February 12, 2013, Aoki gave birth to a girl named Alessandra Linville Bailey with husband James Bailey.[8]